JPS63142063A - Novel bisazo compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (Z is benzene ring, naphthalene ring or carbazole ring; R is H, halogen, lower alkyl, lower alkoxyl or nitro; n is 1-3). EXAMPLE:1,12-Bis[4-( 2-hydroxy-3-phenylcarbamoylnaphthyl-1-azo )phenyl]-1,3,5, 7,9,11-dodecahexaene. USE:Useful as an electrophotographic photosensitive material for high-speed copiers and laser printers, particularly organic semiconductor used in laminated type photosensitive materials. PREPARATION:A tetrazolinium salt expressed by formula II (X is anionic functional group) is subjected to coupling reaction with a coupler expressed by formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel bisazo compound useful as an organic photoconductor and a method for producing the same.

Conventionally, certain azo compounds have been used in organic photoconductors used in laminated photoconductors, which is one form of electrophotographic photoconductor.
It is known to be particularly useful as a charge-generating pigment. As is well known, this laminated photoreceptor has a charge generation layer containing a charge generation pigment as a main component having the ability to generate charge carriers by light on a conductive support, and a charge carrier generated by the charge generation layer on top of the charge generation layer. This photoreceptor is provided with a charge transport layer mainly composed of a charge transport substance that can efficiently inject and further transport charge. Conventionally, examples of azo compounds used in such photoreceptors include those disclosed in Japanese Patent Application Laid-Open No. 47-37543.
benzidine-based bisazo compounds described in JP-A-52-55643, etc.; stilbene-based bisazo compounds described in JP-A-52-8832;
Diphenylhexatriene-based bisazo compounds described in JP-A-222152, diphenylbutadiene-based bisazo compounds described in JP-A-58-222153, and the like are known.

However, conventional laminated photoreceptors using azo compounds generally have low sensitivity and are unsatisfactory as photoreceptors for high-speed copying machines. On the other hand, in recent years, there has been a desire to develop high-sensitivity photoconductors that can cover the wavelength range of semiconductor lasers as photoconductors for laser printers. The reality is that you can't get it. Therefore, it is desired to produce an azo compound useful as an organic photoconductor that overcomes the conventional drawbacks.

An object of the present invention is to provide a highly sensitive electrophotographic photoreceptor that is practical not only for use in high-speed copying machines but also for laser printers.
Particularly, an object of the present invention is to provide a bisane compound useful as an organic photoconductor used in a laminated photoreceptor and a method for producing the same.

One of the features of the present invention is the general formula (I) (where Z represents a benzene ring, a naphthalene ring or a carbazole ring, R may be the same or different, and a hydrogen atom,
halogen atom.

(represents a lower alkyl group, lower alkoxyl group, or nitro group, and n represents an integer of 1, 2, or 3), and the other one is a bisazo compound represented by the general formula ■ x O, N 2 @- ◎+CH=CH), -〇-NI-X
It is characterized by coupling a tetrazonium salt represented by 0 (representing an anionic functional group) with a coupler represented by the general formula shall be. This is a method for producing a bisazo compound represented by the general formula I. Here, the substitute for the anionic functional group X in the general formula (Im) is: ICQ'', B r@, I', B F2
O.

PF&θ, B(C6H5)4', C2O4゜, SO2"
.

Examples include H,C-◎-5Q3'', AsF,'', SbF&e, and preferably BF. It is.

Prior to the present invention, the bisazo compound represented by the general formula (I) is produced as follows. first.

The tetrazonium salt of the general formula (I) as a raw material is
1,12-bis(4-nitrophenyl)-1,3,5,
7,9,11-dodecahexaene (hereinafter referred to as dinitro compound) is reduced to produce 1,12-bis(4-aminophenyl)-1,3,5,7,9,11-dodecahexaene (hereinafter referred to as diamino compound). ) and can be obtained by diazotizing it. Both dinitro compounds and diamino compounds used herein are new substances. The dinitro compound can be produced by the so-called Wittig reaction, in which, for example, 4-nitrosinnamyltriphenylphosphonium bromide and 2,4-hexadiene-1,6-dial are condensed in the presence of a basic catalyst.

The dinitro compound produced by this reaction contains a portion of the cis isomer, which can be used as a reaction crude product as it is or after purification, toluene together with a catalytic amount of iodine.

It can be converted into an all-trans form by heat treatment in an aromatic hydrocarbon solvent such as xylene.

Reduction of the dinitro compound is usually carried out by heating to a temperature of 70 to 120° C. using iron-hydrochloric acid, tin-chloride monohydrochloric acid, etc. as a reducing agent, and the reaction is completed in about 0.5 to 3 hours. In addition, when an iron-hydrochloric acid reducing agent is used, it is preferable to carry out the reaction in an organic solvent such as N,N-dimethylformamide.

Next, diazotization of the diamino compound thus obtained is carried out by dispersing the diamino compound in an inorganic acid such as hydrochloric acid or sulfuric acid, and adding sodium nitrite to this at a temperature of -10 to 20°C. The reaction is completed in about 0.5-3 hours.

This reaction yields a tetrazonium salt of the general formula (n), and by further adding an aqueous solution of borofluoric acid, sodium borofluoride, etc. to this diazotization reaction solution for salt conversion, the tetrazonium salt of the general formula (II) is obtained. The tetrazonium salt of can be obtained.

To prepare the bisazo compound of the present invention using the tetrazonium salt obtained in this way, first, the tetrazonium solution is isolated from the reaction solution, and then it is mixed with N,N-dimethylformamide, dimethylsulfoxide, etc. together with the coupler of the general formula H. What is necessary is to dissolve it in an organic solvent and dropwise add an alkaline aqueous solution such as an aqueous sodium acetate solution thereto at a temperature of about -10 to 40°C to cause a coupling reaction. This reaction is completed in about 5 minutes to 3 hours. After the reaction is completed, the precipitated crystals are collected and purified by an appropriate method such as washing with water and/or an organic solvent, recrystallization, etc.

The desired bisazo compound is obtained. The bisazo compound can also be produced by directly reacting the diazotization reaction solution with a coupler.

Specific examples of the bisazo compound of the present invention produced as described above are shown in Table 1 along with elemental analysis results and infrared absorption spectrum data.

Table-1 Table-1 Table-1 The present invention will be explained below using examples and application examples.

28.7 g of 4-nitrosinnamyltriphenylphosphonium bromide and 2.9 g of 2,4-hexadiene-1,6-dial were placed in 250 ffIQ of dry methanol, and under a nitrogen stream, 14.44 g of a 28% methanol solution of sodium methoxide was added. was added dropwise at 23-26°C. After 0 dropwise addition, which took 1 hour, the mixture was stirred at room temperature for 7 hours, diluted with 200 mm of 50% aqueous methanol solution, and the precipitate was collected.
After washing with water and drying, 9.0 g of ffi product containing cis isomer (
A yield of 87% was obtained.

Next, add this to xylene 200a+Q along with a catalytic amount of iodine.
After heating under reflux for 8 hours in
4-nitrophenyl) -1゜3.5,7,9.11-
7.2 g of dark red needle crystals of dodecahexaene '41)
6 Melting point 250℃ Elemental analysis value (%) HN Actual value 71.81 5.05 6.92 The infrared absorption spectrum (KBr tablet method) is shown in Figure 1. Absorption based on vibration and absorption based on out-of-plane bending vibration of transolefin were observed in 1005.975C■-1.

Dinitro compound 7 obtained as described above, Og t
&D MF 250m Take it to Q and add iron powder 14.
After adding 0 g, add 3.3 mQ of concentrated hydrochloric acid and 1 ml of water while stirring.
Dilute hydrochloric acid consisting of 0 mQ was added, and the mixture was stirred at 80 to 90°C for 4 hours. After cooling to 60° C., a 10% aqueous sodium hydroxide solution was added to make the mixture alkaline, and the insoluble portion was filtered hot with Celite. The solution was diluted with water, and the precipitated crystals were filtered, washed with water, and dried to obtain 5.1 g (yield: 85%) of a diamino compound. Recrystallized from a mixed solvent of DMF-water to give 1,12-bis(4-aminophenyl)-1,3,5
, 7,9,11-dodecahexaene was obtained as dark brown plate-like crystals. Melting point 276°C (decomposition point) Elemental analysis value (%) HN Actual value 84.42 7,13 8.12 The infrared absorption spectrum (KBr tablet method) is shown in Figure 2. Absorption based on the out-of-plane bending vibration of the trans-olefin was observed at 1000.975 cm-'' in the stretching vibration of the class amine.

j' of the tetrazonium salt 4.0 g of the diamino compound obtained as described above was added to dilute sulfuric acid consisting of 7 mfl of concentrated sulfuric acid and 100 Q of water,
After stirring at 60°C for 2 hours.

It was rapidly cooled to =3°C. Next, add 1 part sodium nitrite to this.
．． A solution of 74g dissolved in 5mQ of water was heated at -3 to -2℃ for 4 hours.
It took 0 minutes to drip. Thereafter, the mixture was stirred at the same temperature for 20 minutes, and 200 n+Q of water was added. Traces of insoluble matter were removed by filtration. A 42% aqueous solution of borohydrofluoric acid was added to the filtrate, and the precipitated crystals were collected in an oven and dried. dark red tetrazonium salt 5
．． 5g (87% yield) was obtained. The infrared absorption spectrum is shown in FIG. 3, and absorption based on N2 stretching vibration was observed at 2220 cm-1.

Preparation of Bisazo A of Compound No. 1 in Table 1 above
- 0.35 g of hydroxy-2-naphthoic acid anilide in D
After dissolving MF 130a+ Q and adding 0.34 g of the tetrazonium salt obtained as described above, 2.5 mQ of an 8.6% aqueous sodium acetate solution was dissolved at room temperature.
After stirring at the same temperature for 3 hours, the resulting bisazo pigment was filtered and DMF 15
Washed 5 times with 0+a Q, followed by 2 washes with 150 mQ of water. This was further heated and dried under reduced pressure to form the compound NO.
61 bisazo pigment: 1.12-bis[4-(2-hydroxy-3-phenylcarbamoylnaphthyl-1-azo)phenyl]-1,3,5,7,9,11-dodecahexaene as blue-black powder as 0.50g (yield 89%
) Obtained 0 decomposition point 263°C Elemental analysis (as Cs4H4°N604) CHN Actual value (%) 78.08 4.89 9.20 Calculated value (%) 7g, 35 5.00 9.45 Visible spectrum [ethylenediamine/ DMF (I/9:
vo Q)) :λwax, 596nm The infrared absorption spectrum (KBrBr method) of this product is shown in Figure 4.As can be seen from this figure, there is absorption based on the stretching vibration of C=○ at 1675cm-'', and transduction at 103103O'. Absorption based on out-of-plane bending vibration of the olefin was observed.

Examples 2 to 29 Compounds Nos. 2 to 29 were prepared in the same manner as in Example 1 using couplers corresponding to Compounds Nos. 2 to 29, respectively.
A bisazo compound was prepared.

These elemental analysis results and IR spectrum data are shown in Table-
As shown in 1.

Next, application examples of the bisazo compound of the present invention are shown below.

Application Example: As a charge generating substance, 7.5 parts of a bisazo compound of Compound Nα1 in Table 1 and 500 parts of a 0.5% tetrahydrofuran solution of polyester resin (Vylon 200 manufactured by Toyobo Co., Ltd.) were ground and mixed in a ball mill. The resulting dispersion was applied with a doctor blade onto an aluminum-deposited polyester film and air-dried to form a charge generation layer about 1 μm thick. - Dissolve 2 parts of phenylhydrazone in a 10% tetrahydrofuran solution of polycarbonate resin (Teijin Panlite -1300), apply this solution onto the charge generation layer using a doctor blade, and apply the solution at 80°C for 2 minutes. Then, it was dried at 120℃ for 5 minutes to a thickness of about 20μ.
A charge transport layer of m was formed.

Next, in order to examine the sensitivity of the laminated electrophotographic photoreceptor thus obtained in the visible range, this photoreceptor was tested in a dark place using an electrostatic copying paper tester (Model 5P428, manufactured by Kawaguchi Denki Seisakusho Co., Ltd.). After charging with 6KV corona discharge for 20 seconds, dark decay was performed for 20 seconds, and the surface potential Vo (volt) at this time was measured.
．． A tungsten lamp is irradiated so that the surface potential becomes V.

The time (see) until the value becomes 1/2 was determined, and the half-reduction exposure amount E 1/2 was determined as the sensitivity in the visible range.

As a result, V o = 858 volts, El/2 =:
6. It was IQuxsee.

Thus, it can be seen that the photoreceptor using the bisazo compound of the present invention has extremely high sensitivity in the visible region.

Effects As can be seen from the above explanation, the tetrazonium chloride of the present invention can be used as an organic photoconductor used in electrophotographic photoreceptors, especially laminated photoreceptors, which exhibit high sensitivity for both high-speed copying machines and laser printers. It is extremely useful as a

[Brief explanation of the drawing]

Figures 1 to 3 show infrared absorption spectra of a dinitro compound, a diamino compound, and a tetrazonium salt, which are intermediates for producing the bisazo compound of the present invention, respectively, and Figure 4 shows the infrared absorption spectra of the compound of the above-mentioned coating-1 of the present invention. The infrared iron absorption spectrum of the bisazo compound No. 1 is shown. January 2nd, 1986, the Commissioner of the Patent Office, Kuro 1) Mr. Akio
1. Indication of the case 1986 Patent Application No. 289986 2. Name of the invention Relationship to the case Patent applicant 1-3-6 Nakamagome, Ota-ku, Tokyo (674) Ricoh Co., Ltd. Representative Hama 1) Hiroshi 4. Agent, 4-5 Kojimachi, Chiyoda-ku, Tokyo (102) 5. Compound Nα4 in Table 1 on page 9 of the "Detailed Description of the Invention" column of the amended specification. and Nα5+R
) specific representation of n r 2-QC) I, J as r 2-
CI, J, r4-QC! Correct I3J to r4-CH and J, respectively. that's all

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc.▼ (However, Z represents a benzene ring, naphthalene ring, or carbazole ring, R may be the same or different, and a hydrogen atom
It represents a halogen atom, a lower alkyl group, a lower alkoxyl group or a nitro group, and n represents an integer of 1, 2 or 3. ) A bisazo compound represented by 2. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, X represents an anion functional group.) Tetrazonium salt represented by and general formula III ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, Z , R, and n are the same as in general formula I below) General formula I characterized by a coupling reaction with a coupler represented by ▲ Numerical formulas, chemical formulas, tables, etc. represents a carbazole ring, R may be the same or different, and a hydrogen atom,
It represents a halogen atom, a lower alkyl group, a lower alkoxyl group or a nitro group, and n represents an integer of 1, 2 or 3. ) A method for producing a bisazo compound shown in